Lubricant additive and composition containing same



United States Patent M LUBRICANT ADDITIVE AND COMPOSITION CONTAINING SAME Albert R. Sabol, Munster, Eli W. Blaha, Highland, and Robert E. Karll, Munster, Ind., assignors to Standard Oil Company, Chicago, 111., a corporation of Indiana No Drawing. Filed May 26, 1958, Ser. No. 737,479

17 Claims. (Cl. 252-325) The present invention relates to an improved lubricant additive, and lubricant compositions containing the same, and more particularly relates to an oil-soluble alkaline earth-boron complex of the hydrolyzed reaction product of a phosphorus sulfide and a hydrocarbon containing a high percent of the alkaline earth metal, and to lubricant compositions containing the improved lubricant additive.

Neutralized reaction products of a phosphorus sulfide and a hydrocarbon, particularly olefin polymer, are widely used as detergent-type additives in lubricants, especially in crankcase lubricating oils of internal combustion engines. The use of such additives in lubricant compositions is described in U.S. Patents No. 2,316,080, and No. 2,316,082, issued April 6, 1943, to C. M. Loane et al. Such detergent-type additives are most effective under heavy duty, high temperature conditions of engine operation. However, in engines operating under moderate or light duty service and under intermittent operating conditions, wherein low engine jacket and crankcase temperatures prevail, such detergent additives often are of limited effectiveness in combating sludge conditions of the low-temperature type which may result from extreme oil contamination with combustion chamber blow-by products. For such low-temperature operating conditions lubricant detergent-type additives of higher ratios of alkaline earth metal to phosphorus are desired. Also, it is desirable to provide a low-temperature detergent-type additive which is effective in preventing the corrosion of copper and silver which are components of bearings, etc. in present day internal combustion engmes.

It is an object of the present invention to provide a method of preparing an improved lubricating oil lowtemperature detergent-type additive having a high alkaline earth metal to phosphorus ratio. Another object is to provide a lubricating oil additive having a high alkaline earth metal to phosphorus ratioand which possesses improved detergency properties. Another object of the invention is to provide as an additive an alkaline earthcontaining neutralized reaction product of a phosphorus sulfide and a hydrocarbon having a high alkaline earth content, which additive has improved detergency and silver and/ or copper corrosion-inhibiting properties. Still another object of the invention is to provide a lubricant composition containing the improved additive. Other objects and advantages of the invention will become apparent from the following description thereof.

In accordance with the present invention, the fore going objects are attained by the use of an oil-soluble additive complex obtained by reacting a phosphorus sulfide, e.g. phosphorus pentasulfide, with a normally nongaseous hydrocarbon, as hereinafter described, hydrolyzing the resultant reaction product, and subsequently forming a complex by reacting the hydrolyzed reaction product with boric acid, anhydride or ester and a basic alkaline earth compound in the presence of water and an alkanol of l to 3 carbon atomsor a mixture of such alkanols and a phenol or an alkylated phenol having from about to about 12 carbon atoms in the alkyl group or groups under the hereinafter described conditions.

In the preparation of the phosphorus sulfide-hydrocarbon reaction products, the hydrocarbon is reacted with a phosphorus sulfide, such as P S P S P 8 or other 3,002,924 latented Oct.,3, 1961 phosphorus sulfides, and preferably phosphorus pentasul- The hydrocarbon constituent of this reaction is suitably a normally non-gaseous hydrocarbon such as is described in detail in U.S. 2,316,080, 2,316,082, and 2,316,088, each issued to Loane et al. on April 6, 1943. While the hydrocarbon constituent of this reaction can be any of the type hereinafter described, it is preferably a mono-olefin hydrocarbon polymer resulting from the polymerization of low molecular weight mono-olefinic hydrocarbons or isomono-olefinic hydrocarbons, such as propylene, butylenes, and amylenes or the copolymers obtained by the polymerization of hydrocarbon mixtures containing isomono-olefins and mono-olefins or mixtures of olefins in the presence of a catalyst, such as sulfuric acid, phosphoric acid, boron fluoride, aluminum chloride or other similar halide catalysts of the Friedel-Crafts type.

The polymers employed are preferably mono-olefin polymers or mixtures of mono-olefin polymers and isomono-olefin polymers having molecular weights ranging from about 150 to about 50,000 or more, and preferably from about 300 to about 10,000. Such polymers can be obtained, for example, by the polymerization in the liquid phase of a hydrocarbon mixture containing mono-olefins and isomono-olefins such as butylene and isobutylene at a temperature of from about F. to about F. in the presence of a metal halide catalyst of the Friedel-Crafts types such as, for example, boron fluoride, aluminum chloride, and the like. In the preparation of these polymers we may employ, for example, a hydrocarbon mixture containing isobutylene, butylenes and butanes recovered from petroleum gases, especially those gases produced in the cracking of petroleum oils in the manufacture of gasoline.

Essentially paratfinic hydrocarbons such as bright stock residuums, lubricating oil distillates, petrolatums, or paraffin waxes, may be used. There can also be employed the condensation products of any of the foregoing hydrocarbons, usually through first halogenating the hydrocarbons, with aromatic hydrocarbons in the presence of anhydrous inorganic halides, such as aluminum chloride, zinc chloride, boron fluoride, and the like.

Other preferred olefins suitable for the preparation of the herein described phosphorus sulfide reaction products are olefins having at least 20 carbon atoms in the molecule of which from about 13 carbon atoms to about 18 carbon atoms, and preferably at least 15 carbon atoms, are in a long chain. Such olefins can be obtained by the dehydrogenation of paraflins, such as by the cracking of paraffin waxes or by the dehalogenation of alkyl halides, preferably long chain alkyl halides, particularly halogenated paraffin waxes.

Also contemplated within the scope of the present invention are the reaction products of a phosphorus sulfide with an aromatic hydrocarbon, such as for example, benzene, naphthalene, toluene, xylene, diphenyl and the like or with an alkylated aromatic hydrocarbon, such as for example, benzene having an alkyl substituent having at least four carbon atoms, and preferably at least eight carbon atoms, such as long chain paratfin wax.

The phosphorus sulfide-hydrocarbon reaction product is prepared by reacting the phosphorus sulfide, e.g. P 8 with the hydrocarbon at a temperature of from about F. to about 600 F., preferably from about 300 F. to about 500 F using from 1% to about 50%, preferably from about 5% to about 25% of phosphorus sulfide; the reaction is carried out in from about one to about ten hours. It is preferable to use an amount of the phosphorus sulfide that will completely react With the hydro carbon so that no further purification is necessary; however, an excess of the phosphorus sulfide can be used, andthe unreacted material separated by filtration. The

reaction, if desired, can be carried out in the presence of a sulfurizing agent such as sulfur or a halide of sulfur as described in U.S. 2,316,087, issued to J. W. Gaynor et a1. April 6, 1943. It is advantageous to maintain a non-oxidizing atmosphere, for example an atmosphere of nitrogen, in the reaction vessel. The reaction product obtained is then hydrolyzed at a temperature of from about 200 F. to about 500 F., preferably at a temperature of about 300 F.400 F. by suitable means, such as for example, by introducing steam through the reaction mass. The hydrolyzed product, containing inorganic phosphorus acids formed during the hydrolysis, can be used as such in the subsequent neutralization stage; or it can be substantially freed of the inorganic phosphorus acids by contacting with an adsorbent material such as Attapulgus clay, fullers earth and the like at a temperature of 100 F.-500 F. as fully described and claimed in U.S. 2,688,612, issued to R. Watson September 7, 1954, or by extraction with phenol or an alkanol of 1 to carbon atoms in admixture with water as described and claimed in Lemmon et a1. U.S. application Serial No. 588,262, filed May 31, 1956, now U.S. Patent No. 2,843,- 579.

The complex of the hydrolyzed reaction product of the phosphorus sulfide and the hydrocarbon is then formed by neutralization with a basic alkaline earth compound in the presence of a boron compound, above described, water, an alkanol of 1 to 3 carbon atoms, or a mixture of such alkanol and phenol or an alkylated phenol, at the reflux temperature of the alkanol, namely from about 155 F. to about 185 F. The basic alkaline earth compound can be for example the oxide, hydroxide, carbonate or sulfide of calcium, barium, strontium or magnesium, although barium oxide is preferred. While it is preferred to use boric acid, boric acid anhydride or a boric acid ester which decomposes to give boric acid can be used.

Examples of the organic mono-hydroxy compound of the classes above described used can be methanol, ethanol, propanol or isopropanol, phenol, amyl phenol, octyl phenol, nonyl phenol, dodecyl phenol, etc. of which methanol or a mixture of methanol and nonyl phenol are preferred.

The formation of the complex can be carried out directly with the phosphorus sulfide-hydrocarbon reaction product; however, to facilitate handling, it is preferable to form a slurry of the unhydrolyzed phosphorus sulfidehydrocarbon reaction product in a lubricating oil, such as for example, a 5W oil, although any suitable normally liquid hydrocarbon or oil diluent can be used.

The complex is suitably formed by adding to the slurried hydrolyzed phosphorus sulfide-hydrocarbon reaction product from about 0.1 mole to about 4.0 moles of the boric acid, anhydride or ester, and neutralizing the mixture with from about 1.0 mole to about 4.0 moles of the basic alkaline earth compound in the presence from about 0.5 mole to 2.0 moles water and from about 2 moles to about moles of the alkanol, or the mixture of said alkanol and from about 0.1 mole to about 3 moles of phenol or alkylated phenol, per mole of the basic alkaline earth compound, and heating the reaction mixture at the reflux temperature of the alkanol for a period of from about 1 hour to about 10 hours. When using a mixture of said monohydroxy compounds, the alkanol and phenol compound are used in the ratio of from about 2:1 to about 10:1. The reaction vessel is equipped with a reflux condenser to avoid the loss of alkanol phenol and water vapors. After heating the reflux temperature for the required time, the temperature is raised to about 250 F.400 F., preferably 320 F.350 F., the alkanol, phenol, and water distilled off, and the resultant neutralized complex recovered, such as by filtering through a suitable adsorbent material such as for example Celite, Attapulgus clay, fullers earth and the like.

The following specific examples illustrate the preparation of the herein described additive complex. It is to be understood that the examples are for the purpose of illustration only and are not to be regarded as a limitation of the present invention.

EXAMPLE I A butylene polymer having a molecular weight of about 780 was reacted with 15.5% (wt) P 8 at about 450 F. for about 5.5 hours, the productv hydrolyzed by steaming at 300 F. for about 5 /2 hours, and the resultant hydrolyzed product diluted with an SAE-5W motor oil base to give a product having a phosphorus content of 2.51%, a mixture consisting of 1235 grams (48.75%) of the diluted hydrolyzed product, 1235 grams (48.75%) of an SAE-5W motor oil, and 63.4 grams (2.5%) of boric acid was treated with 382 grams (2.5 moles Ba) barium oxide (sufiicient to give about 9.5 to 1 Ba:P ratio) in the presence of 36 ccs. water (0.8 m./m. BaO) and 710 ccs. methanol (7 m./m. BaO) at the reflux temperature of the methanol (about 160 F.) for 3 hours. The product was then heated to 300 F., the alcohol and water distilled OE and the remaining product filtered through Celite. The filtrate contained 12.7% barium, 1.35 phosphorus, 0.66% sulfur and 0.45% boron.

EXAMPLE II A polybutene having an average molecular weight of about 780 and a Saybolt Universal viscosity at 210 F. of about 1000 seconds was reacted with 15.5% (wt.) at 450 F. for about 5.5 hours, and the product hydrolyzed by steaming at 300 F. for about 5 /2 hours. The resultant hydrolyzed reaction product contained 4.4% phosphorus and 2.9% sulfur. Seven hundred and four grams of the hydrolyzed product (containing 1 mole of phosphorus) was diluted with sufiicient solvent extracted SAE-5W mineral oil to give a product containing 1.26% phosphorus. To the hydrolyzed unneutralized product was added 70 grams of boric acid (1.1 moles boron per mole phosphorus), and the mixture neutralized with 280 grams BaO (sufficient to give an 8:1 Ba:P ratio) in the presence of a mixture of 520 ccs. methanol (7 moles methanol/mol BaO), and 26 ccs. water (0.8 mole H o/mole BaO). The reaction mixture was then refluxed for 3 hours at about 160 F., the temperature then raised to 320350 F., the water and methanol distilled off and the distilled product filtered through Celite. The resultant filtrate contained 0.44% boron, 1.13% phosphorus, 0.66% sulfur, and 8.72% barium.

EXAMPLE III One thousand grams (0.8 mole phosphorus) of the hydrolyzed reaction product of a butylene polymer having a molecular weight of about 780 and P 8 as described in Example I, was diluted with 1000 grams of a 5W motor oil base to give a product containing 1.55% phosphorus. One hundred grams (1.3 moles) of boric acid were added to the diluted hydrolyzed reaction product and the mixture neutralized with 400 grams (2.6 moles) barium oxide in the presence of grams (0.45 mole) nonyl phenol, 500 cc. (12.6 moles) methanol and 25 cc. (1.4 moles) water and the reaction mixture heated at -160 F. (reflux temperature of the methanol) under reflux conditions for three hours. The temperature was then raised to 300 F. to remove the methanol, water and some nonyl phenol, and the product then filtered through Celite. The filtrate contained 11.14% barium, 1.03% phosphorus and 0.58% boron.

EXAMPLE IV A polybutene having an average molecular weight of about 780 and a Saybolt Universal viscosity at 210 F. of about 1000 seconds was reacted with 15 /z% (wt.) P S at 450 for about 5.5 hours and the product hydrolyzed by steaming at 300 F. for about 5 /2 hours. Seven hundred and four grams (containing 1 mole of phosphorus) of the resultant hydrolyzed material were diluted with sutficient. solvent extracted SAE-SW mineral oil to give a product containing 1.26% phosphorus." To the hydrolyzed unneutralized product were added 140 grams of boric acid (2.25 mole boron per mole phosphorus), and the mixture neutralized with 382 grams BaO (suflicient to give an 11:1 Ba:P ratio) in the presence of a mixture of 710 cc. methanol (7 mole methanol per mole BaO) and 110 cc. nonyl phenol (0.5 mole phenol per mole phosphorus) and 36 cc. water (0.8 mole H O per mole BaO). The mixture was refluxed 3 hours at about 160 F., and the temperature then raised to 320-350 F., to distil oi the Water, methanol, and nonyl phenol. The product was then filtered through Celite. The resultant filtrate contained 0.7% boron, 1.0% phosphorus, 0.7% sulfur, and 10.9% barium.

The herein described additive of the present invention can be used in amounts of from about 0.01% to about 15%, preferably from about 0.25% to about in lubricant base oils, such as mineral lubricating oils, syn thetic hydrocarbon lubricating oils, synthetic lubricating oils or the polyalkylene oxide type, for example, the Ucon oils marketed by Carbide and Carbon Corporation, as well as polycarboxylic acid ester type synthetic lubricating oils such as the esters of adipic acid, sebacic acid, azelaic acid, etc. While the additive of the present invention can be used alone in the base oil, it can be used in combination with small amounts, e.g. 0.02% to 10%, of other lubricant addition agents, such as zinc dialkyl dithiophosphates, sulfurized terpene, e.g. sulfurized dipentene, viscosity index improvers, pour point depressors, rust inhibitors, etc.

The low-temperature detergency property of the complex of the present invention is demonstrated [by the data in Table I, below, which data were obtained in the engine test designed to determine the low-temperature detergency of motor oils. The test, known as the Ll test, having C.R.C. designation L-l-545 is fully described in C.R.C. Handbook, 1946 edition, of the Coordinating Research Council, New York. Briefly, the test is conducted in a lA-Sl single cylinder Caterpillar engine operating at 1000 rpm. at a load of 19.8 B.H.P. with an oil temperature to bearings of l45-l50 F. and a Water jacket outlet temperature of 175 180 F. and an inlet temperature of 10-15 F. below the outlet temperature. The test is run for 480 hours, with inspections at the end of each 120, 240' and 480 hour periods for carbon in the ring grooves, expressed in terms of percent groove filled.

The following lubricant compositions were subjected to the above test and the data in Table I obtained.

Sample A-SAE 30 base motor oil containing 5% of a barium oxide neutralized hydrolyzed reaction product of a polybutene of about 780 molecular weight and P 8 and 0.625 of a zinc dialkyl dithiophosphate Sample B-fiSAE 30 base motor oil containing 5.5% of product of Example II (equivalent to 4.3% of the barium neutralized hydrolyzed polybuteneP S' reaction product of sample A) and 1.25 of zinc dialkyl dithiophosphate 1 Sample HAE 30 base motor oil containing 3.8% of product of Example II and 0.625% zinc dialkyl dithiophosphate 1 Sample D--SAE 30 base motor oil containing 2.45% product of Example II and 0.625% zinc dialkyl dithiophosphate 1 p Sample E-SAE 30 base motor oil containing 3.5% product of Example III and 0.75% zinc dialkyl dithiophosphate 1 Sample FSAE 30 base motor oil containing 3.2% product of Example I and 0.75% zinc dialkyl dithiophosphate 1 Prepared from a mixture of isopropanol and methyl isobutyl carbine].

Detergcney Percent Top I131mg Groove ar on 240 Hrs. 480 Hrs.

Hrs.

In each of the tests, the lacquer was zero percent. In the L-l test a carbon value of less than 25% is passing.

In the L-4 engine test, designed for evaluating the oxidation and bearing corrosion characteristics of motor oils conducted according to the procedure specified by the C.R.C. designation L4 -545, C.R.C. Handbook, 1946 edition, Coordinating Lubricants Research Council, New York, sample F, supra had a varnish rating of 9.8 and a bearing weight loss of 0.066 (average of 3); the base oil alone in this test has a varnish rating of 6.5 and an average bearing Weight loss of 1.5. Briefly, the test procedure involves the operation of a special six-cylinder automotive engine at constant speed and load for a period of 36 hours. The engine is operated at 3150 r.p.m.i25 at an engine load of 30 B.H.P.: with a jacket coolant outlet temperature of 200 F.i2 and an inlet temperature of 190 F. min. Oil sump temperature of 265280 F. (depending on the base oil viscosity) is used. At the end of the test period, the engine is disassembled and inspected for deposits and rated on a cleanliness scale of 0 to 10; a rating of 10 denoting a clean engine free of deposits. The bearings are weighed to determine the weight loss due to corro- S1011.

Concentrates of a suitable oil base containing more than 15%, for example up to 50% or more, of the additive of the present invention, alone or in combination With other desired additives, can be used for blending, with hydrocarbon oils or other oils in the proportions desired for the particular conditions of use to give a finished product containing from 0.01% to about 15% of the additive of the present invention.

Percentages given herein and in the appended claims are weight percentages unless otherwise stated.

Although the present invention has been described with reference to specific preferred embodiments thereof, the invention is not to be considered as limited thereto but includes within its scope such modifications and variations as come within the spirit of the appended claims.

We claim:

1. As a new composition of matter, the oil-soluble neutralized alkaline earth and boron-containing complex of the reaction product of a phosphorus sulfide and a normally non-gaseous hydrocarbon, said neutralized complex being obtained by the process comprising reacting from about 1% to about 50% of a phosphorus sulfide and a normally non-gaseous hydrocarbon at a temperature of from about F. to about 500 F., hydrolyzing the resultant reaction product, neutralizing the resultant hydrolyzed reaction product with from about 1 mole to about 4 moles of an inorganic basic alkaline earth compound per mole of phosphorus in the presence of from about 0.1 mole to about 4 moles of a boron compound per mole of phosphorus selected from the group consisting of boric acid, boric acid anhydride and a boric acid ester, from about 0.5 mole to about 2.0 moles Water per mole of alkaline earth compound and from about 2 moles to about 10 moles per mole of an alkaline earth compound of an organic monohydroxy material selected from the group consisting of an alkanol having not more than three carbon atoms, and a mixture of said alkanol and a phenol, while heating the mixture at the reflux temperature of said alkanol for a period of from 1 hour to about hours, raising the temperature of the mixture from about 250 F. to about 400 F. and recovering the resultant neutralized complex product.

2. A new composition of matter as described in claim 1 in which the boron compound is boric acid.

3. A new composition of matter as described in claim 1 in which the alkanol is methanol.

4. A new composition of matter as described in claim 1 in which the hydroxy material is a mixture of methanol and phenol.

5. A new composition of matter as described in claim 1 in which the basic alkaline earth compound is BaO.

6. A new composition of matter as described in claim 1 in which the basic alkaline earth compound is CaO.

7. As a new composition of matter the oil-soluble neutralized barium and boron-containing complex of the reaction product of a phosphorus sulfide and an olefin polymer, said neutralized complex, being obtained by the process comprising reacting from about 1% to about 50% of a phosphorus sulfide with an olefin polymer at a temperature of from about 150 F. to about 500 F. hydrolyzing the resultant reaction product, neutralizing the resultant hydrolyzed product with from about 1 mole to about 4 moles barium oxide per mole of phosphorus in the presence of from about 0.1 mole to about 4 moles boric acid, per mole of phosphorus, from about 0.5 mole to about 2.0 moles Water, per mole of barium oxide, from about 2 moles to about 10 moles methanol, per mole of barium oxide, and from about 0.1 mole to about 2 moles phenol per mole of barium oxide while heating the mixture at the reflux temperature of said methanol for a period of from about 1 hour to about 10 hours, raising the temperature of the mixture to from about 250 F. to about 400 F. and filtering the resultant neutralized complex.

8. A new composition of matter as described in claim 6 in which the olefin polymer is a polybutene.

9. A lubricant composition comprising a major proportion of a normally liquid olcaginous lubricant and from about 0.01% to about of the oil-soluble neutralized alkaline earth and boron-containing complex of the reaction product of a phosphorus sulfide and a normally nongaseous hydrocarbon, said neutralized complex being obtained by the process comprising reacting from about 1% to about 50% of a phosphorus sulfide and a normally non-gaseous hydrocarbon at a temperature of from about 150 F. to about 500 F., hydrolyzing the resultant reaction product, neutralizing the resultant hydrolyzed mixture with from about 1 mole to about 4 moles of an inorganic basic alkaline earth compound per mole of phosphorus in the presence of from about 0.1 mole to about 4 moles of a boron compound per mole of phosphorus selected from the group consisting of boric acid, boric acid anhydride and a boric acid ester, from about 0.2 mole to about 2.0 moles water, per mole alkaline earth compound and from about 2 moles to about 10 moles per mole alkaline earth compound of an organic monohydroxy material selected from the group consisting of alkanol having not more than three carbon atoms and a mixture of said alkanol and a phenol, while heating the mixture at the reflux temperature of said alkanol for a period of from 1 hour to 10 hours, raising the temperature of the mixture to from about 250 F. to about 400 F. and recovering the resultant neutralized complex.

10. A lubricant composition as described in claim 9 in which the boron compound is boric acid.

11. A lubricant composition as described in claim 9 in which the alkanol is methanol.

12. A lubricant composition as described in claim 9 8 in which the organic monohydroxy material is a mixture of methanol and phenol.

13. A lubricant composition as described in claim 9 in which the basic alkaline earth compound is BaO.

14. A lubricant composition as described in claim 9 in which the basic alkaline earth compound is CaO.

15. A lubricant composition comprising a major proportion of a hydrocarbon lubricating oil and from about 0.01% to about 15% of the oil-soluble neutralized barium and boron-containing complex of the reaction product of a phosphorus sulfide and an olefin polymer, said neutralized complex being obtained by the process comprising reacting from about 1% to about 50% of a phosphorus sulfide with an olefin polymer at a temperature of from about F. to about 500 F, hydrolyzing the resultant reaction product, adding from about 0.1 mole to about 4 moles boric acid per mole of phosphorus to the resultant hydrolyzed reaction product, neutralizing the mixture with from about 1 mole to about 4 moles barium oxide per mole of phosphorus in the presence of from about 0.5 mole to about 1.5 moles water per mole alkaline earth oxide and a mixture of from about 2 mols to about 10 mols methanol per mole of barium oxide and from about 0.1 mole to about 2 moles phenol per mole of barium oxide While heating the mixture at the reflux temperature of methanol for a period of from about 1 hour to about 10 hours, raising the temperature of the mixture to from about 250 F. to about 400 F. and filtering the resultant neutralized complex.

16. A lubricant composition as described in claim 15 in which the olefin polymer is a polybutene.

17. An addition agent concentrate for lubricating oils consisting essentially of a lubricating oil containing more than 15% of an oil-soluble neutralized alkaline earth and boron-containing complex of the reaction product of a phosphorus sulfide and a normally non-gaseous hydrocarbon, said neutralized complex being obtained by the process comprising reacting from about 1% to about 50% of a phosphorus sulfide and a normally non-gaseous hydrocarbon at a temperature of from about 150 F. to about 500 !F., hydrolyzing the resultant reaction prod uct, neutralizing the resultant hydrolyzed reaction product with from about 1 mole to about 4 moles of an inorganic basic alkaline earth compound per mole of phosphorus in the presence of from about 0.1 mole to about 4 moles of a boron compound per mole of phosphoius selected from the group consisting of boric acid, boric acid anhydride and a boric acid ester, from about 0.5 mole to about 2 moles water per mole of the alkaline earth compound, and from about 2 moles to about 10 moles per mole of the alkaline earth compound of an organic monohydroxy material selected from the group consisting of an alkanol having not more than three carbon atoms, and a mixture of said alkanol and a phenol, while heating the mixture at the reflux temperature of said alkanol for a period of from 1 hour to about 10 hours, raising the temperature of the mixture from about 250 F. to about 400 F. and recovering the resultant neutralized complex product, said concentrate being capable of dilution with a lubrication oil to form a homogenous mixture containing from about 0.01% to about 15% of said complex.

References Cited in the file of this patent UNITED STATES PATENTS 2,053,474 Graves Sept. 8, 1936 2,346,156 Farrington et al Apr. 11, 1944 2,688,612 Watson Sept. 7, 1954 2,806,022 Sabol Sept. 10, 1957 2,900,376 Sabol et al. Aug. 18, 1959 

1. AS A NEW COMPOSITION OF MATTER, THE OIL-SOLUBLE NEUTRALIZED ALKALINE EARTH AND BORON-CONTAINING COMPLEX OF THE REACTION PRODUCT OF A PHOSPHORUS SULFIDE AND A NORMALLY NON-GASEOUS HYDROCARBON, SAID NEUTRALIZED COMPLEX BEING OBTAINED BY THE PROCESS COMPRISING REACTING FROM ABOUT 1% TO ABOUT 50% OF A PHOSPHORUS SULFIDE AND A NORMALLY NON-GASEOUS HYDROCARBON AT A TEMPERATURE OF FROM ABOUT 150*F., HYDROLYZING THE RESULTANT REACTION PRODUCT, NEUTRALIZING THE RESULTANT HYDROLYZED REACTION PRODUCT WITH FROM ABOUT 1 MOLE TO ABOUT 4 MOLES OF AN INORGANIC BASIC ALKALINE EARTH COMPOUND PER MOLE OF PHOSPHORUS IN THE PRESENCE OF FROM ABOUT 0.1 MOLE TO ABOUT 4 MOLES OF A BORON COMPOUND PER MOLE OF PHOSPHORUS SELECTED FROM THE GROUP CONSISTING OF BORIC ACID, BORIC ACID ANHYDRIDE AND A BORIC ACID ESTER, FROM ABOUT 0.5 MOLE TO ABOUT 2.0 MOLES WATER PER MOLE OF ALKALINE EARTH COMPOUND AND FROM ABOUT 2 MOLES TO ABOUT 10 MOLES PER MOLE OF AN ALKALINE EARTH COMPOUND OF AN ORGANIC MONOHYDROXY MATERIAL SELECTED FROM THE GROUP CONSISTING OF AN ALKANOL HAVING NOT MORE THAN THREE CARBON ATOMS, AND A MIXTURE OF SAID ALKANOL AND A PHENOL, WHILE HEATING THE MIXTURE AT THE REFLUX TEMPERATURE OF SAID ALKANOL FOR A PERIOD OF FROM 1 HOUR TO ABOUT 10 HOURS, RAISING THE TEMPERATURE OF THE MIXTURE FROM ABOUT 250*F. TO ABOUT 400*F. AND RECOVERING THE RESULTANT NEUTRALIZED COMPLEX PRODUCT. 